The present invention concerns novel 3-(2,6-disubstituted phenyl)-5-(4- or 5-arylthien-2- or -3-yl)-1,2,4-triazoles and their use in controlling lepidoptera, coleoptera, mites and other sucking pests. This invention also includes new synthetic procedures, intermediates for preparing the compounds, pesticide compositions containing the compounds, and methods of controlling lepidoptera, coleoptera, mites and sucking pests using the compounds.
There is an acute need for new insecticides and acaricides. Insects and mites are developing resistance to the insecticides and acaricides in current use. At least 400 species of arthropods are resistant to one or more insecticides. The development of resistance to some of the older insecticides, such as DDT, the carbamates, and the organophosphates, is well known. But resistance has even developed to some of the newer pyrethroid insecticides and acaricides. Therefore a need exists for new insecticides and acaricides, and particularly for compounds that have new or a typical modes of action.
A number of 3,5-diphenyl-1H-1,2,4-triazole derivatives have been described in the literature as having acaricidal activity (U.S. Pat. No. 5,482,951; JP 8092224, EP 572142, JP 08283261). U.S. Pat. No. 6,015,826 discloses certain 3-(substituted phenyl)-5-(thienyl)-1,2,4-triazoles and their use in controlling certain insects and mites, viz., aphids, mites and whiteflies. The present invention provides novel compounds with broad-spectrum activity against lepidoptera and coleoptera in addition to mites and other sucking pests.
This invention concerns compounds especially useful for the control of lepidoptera, coleoptera, mites and other sucking pests. More specifically, the invention concerns compounds of the formula (1) 
wherein
Q represents 
X and Y independently represent Cl or F;
R1 and R2 independently represent H, C1-C6 alkyl or halogen, provided that when Q is Q1 or Q3, then R1 and R2 are not both H;
R3 represents C1-C3 alkyl;
R4 represents halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C6 alkoxyalkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 halothioalkyl, C3-C6 alkenyloxy, or phenoxy;
R5 represents H, halogen or a C1-C6 alkyl ether or haloalkyl ether, which, when taken together with R4, forms a 5- or 6-membered ring containing 1 or 2 oxygen atoms;
or a phytologically acceptable acid addition salt thereof.
Preferred compounds of formula (1) include the following classes:
(1) Compounds of formula (1) wherein X and Y are both F.
(2) Compounds of formula (1) wherein X and Y are both Cl.
(3) Compounds of formula (1) wherein X is F and Y is Cl (more preferred).
(4) Compounds of formula (1) wherein Q is Q1 or Q3.
(5) Compounds of formula (1) wherein Q is Q2.
(6) Compounds of formula (1) wherein R1 is CH3, CH2CH3 or Cl when Q is Q1 or Q3, more preferably R1 is CH3.
(7) Compounds of formula (1) wherein R1 is H, CH3, CH2CH3, Cl or Br when Q is Q2, more preferably R1 is H or CH3.
(8) Compounds of formula (1) wherein R2 is H, CH3, CH2CH3, Cl or Br, more preferably R2 is H or CH3.
(9) Compounds of formula (1) wherein R4 is F, Cl, CF3, haloalkoxy or phenoxy, more preferably R4 is haloalkoxy.
(10) Compounds of formula (1) wherein R4 is in the 4-position of the phenyl ring.
(11) Compounds of formula (1) wherein R5 is H, F, Cl, or CF3.
(12) Compounds of formula (1) wherein R3 is CH3.
It will be appreciated by those skilled in the art that the most preferred compounds are generally those which are comprised of combinations of the above preferred classes.
The invention also provides new processes and intermediates for preparing compounds of formula (1) as well as new compositions and methods of use, which will be described in detail hereinafter.
Throughout this document, all temperatures are given in degrees Celsius, and all percentages are weight percentages unless otherwise stated.
Unless specifically limited otherwise, the terms xe2x80x9calkylxe2x80x9d and xe2x80x9calkenylxe2x80x9d, as well as derivative terms such as xe2x80x9calkoxyxe2x80x9d, xe2x80x9calkenyloxyxe2x80x9d and xe2x80x9cthioalkylxe2x80x9d, as used herein, include within their scope straight chain, branched chain and cyclic moieties. The term xe2x80x9calkenylxe2x80x9d is intended to include one or more unsaturated bonds.
Unless specifically limited otherwise, the term xe2x80x9chalogenxe2x80x9d, as well as derivative terms such as xe2x80x9chaloxe2x80x9d, as used herein, refers to fluorine, chlorine, bromine, and iodine. Preferred halogens are fluorine and chlorine.
The terms xe2x80x9chaloalkylxe2x80x9d and xe2x80x9chaloalkenylxe2x80x9d refer to alkyl and alkenyl groups substituted with from one up to the maximum possible number of halogen atoms. The terms xe2x80x9chaloalkoxyxe2x80x9d and xe2x80x9chalothioalkylxe2x80x9d refer to alkoxy and thioalkyl groups substituted with from one up to the maximum possible number of halogen atoms.
The term xe2x80x9calkoxyalkoxyxe2x80x9d refers to an alkoxy group substituted with an alkoxy group. The term xe2x80x9calkyl etherxe2x80x9d refers to an alkylene oxide group which can be bonded either through the carbon or the oxygen atom.
Unless otherwise indicated, when it is stated that a group may be substituted with one or more substituents selected from an identified class, it is intended that the substituents may be independently selected from the class.
Synthesis
Compounds of formula (1) can be prepared by the methods illustrated in Scheme A: 
wherein X, Y, R1, R2, R3, R4 and R5 are defined as in formula (1).
In step a of Scheme A, the compound of formula (A) is coupled with the acid chloride of formula (B) to provide acyl thioimidate of formula (C). Pyridine is the preferred base for coupling, however any organic or inorganic base can be used. Acid chlorides of formula (B) are prepared from corresponding carboxylic acids of formula (G) 
which are either commercially available or are readily made through known procedures. 
Thioimidates (A) are readily available through alkylation of the corresponding thioamides (H) which themselves are commercially available or can be made from the amide (Phosphorus Sulfur, 1985, 25, 297-305) or nitrile (Chem.-Ztg. 1980, 104, 365; J. Chem. Soc. 1952, 742; Can. J. Chem. 1985, 63, 3075).
In the cyclization step b of Scheme A, the compound of formula (C) can be reacted with hydrazine or a substituted hydrazine in toluene at 25 to 110xc2x0 C. to afford the triazole intermediate (D) in good yield with a high degree of regiospecificity. Instead of toluene other aprotic solvents such as tetrahydrofuran (THF) can also be used.
In step c of Scheme A, the compound of formula (D) can be brominated with bromine in acetic acid in the presence or absence of sodium acetate at 25xc2x0 C. to refluxing temperature to afford the compound of formula (E).
In the Suzuki coupling step d of Scheme A, the compound of formula (E) can be reacted with an appropriately substituted R4/R5xe2x80x94boronic acid to provide the compound of formula (F). The coupling can be carried out in an acetonitrile/water mixture or ethanol, at a temperature in the range from ambient to refluxing. Catalytic amounts of dichlorobis(triphenylphosphine)palladium(II) or tetrakis(triphenylphosphine)palladium(0) are typically used for coupling, however other Pd(II) or Pd(0) catalysts can also be used. Typically sodium carbonate is used as a base in the reaction, however other inorganic bases such as potassium carbonate or organic bases such as triethylamine can also be used.
Alternatively, compounds of formula (1) can also be prepared by the methods illustrated in Scheme B: 
wherein X, Y, R1, R2, R3, R4 and R5 are defined as in formula (1).
In step a of Scheme B, the compound of formula (A) is coupled with the acid chloride of formula (Bxe2x80x2) to provide acyl thioimidate of formula (Cxe2x80x2) in a similar fashion as described for step a in Scheme A. Acid chlorides of formula (Bxe2x80x2) are prepared from corresponding carboxylic acids of formula (Gxe2x80x2) 
which are readily made through known procedures.
The cyclization step b of Scheme B is performed in a similar fashion as step b of Scheme A to afford the triazole intermediate (E) in good yield with a high degree of regioselectivity.
In step c of Scheme B, the Suzuki coupling was performed in a similar fashion as step d of Scheme A to afford the compound of formula (F).
Alternatively, compounds of formula (1) can also be prepared by the methods illustrated in Scheme C: 
wherein X, Y, R1, R2, R3, R4 and R5 are defined as in formula (1).
In step a of Scheme C, the compound of formula (A) is coupled with the acid chloride of formula (Bxe2x80x3) to provide acyl thioimidate of formula (Cxe2x80x3) in a similar fashion as described for step a in Scheme A. Acid chlorides of formula (Bxe2x80x3) are prepared from corresponding carboxylic acids of formula (Gxe2x80x3) 
which are readily made through known procedures.
The cyclization step b of Scheme C is performed in a similar fashion as step b of Scheme B to afford the triazole (F).